CN102993782B - Preparation method of polyurethane acrylate oligomer surface modified silica - Google Patents
Preparation method of polyurethane acrylate oligomer surface modified silica Download PDFInfo
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- CN102993782B CN102993782B CN201210533559.1A CN201210533559A CN102993782B CN 102993782 B CN102993782 B CN 102993782B CN 201210533559 A CN201210533559 A CN 201210533559A CN 102993782 B CN102993782 B CN 102993782B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 8
- 229920002635 polyurethane Polymers 0.000 title abstract 3
- 239000004814 polyurethane Substances 0.000 title abstract 3
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 76
- 230000004048 modification Effects 0.000 claims abstract description 43
- 238000012986 modification Methods 0.000 claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 239000012948 isocyanate Substances 0.000 claims abstract description 11
- 150000002513 isocyanates Chemical group 0.000 claims abstract description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 9
- 238000003980 solgel method Methods 0.000 claims abstract description 8
- 229960001866 silicon dioxide Drugs 0.000 claims description 61
- 235000012239 silicon dioxide Nutrition 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 38
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 12
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 12
- 230000018044 dehydration Effects 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- -1 acrylic ester Chemical class 0.000 claims description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- KHLRJDNGHBXOSV-UHFFFAOYSA-N 5-trimethoxysilylpentane-1,3-diamine Chemical compound CO[Si](OC)(OC)CCC(N)CCN KHLRJDNGHBXOSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229960004756 ethanol Drugs 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 claims description 2
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 claims description 2
- VNBLTKHUCJLFSB-UHFFFAOYSA-N n-(trimethoxysilylmethyl)aniline Chemical compound CO[Si](OC)(OC)CNC1=CC=CC=C1 VNBLTKHUCJLFSB-UHFFFAOYSA-N 0.000 claims description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical group CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 239000002105 nanoparticle Substances 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 229920001971 elastomer Polymers 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
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- 239000004033 plastic Substances 0.000 abstract description 2
- 239000005060 rubber Substances 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 abstract 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000002114 nanocomposite Substances 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 238000000016 photochemical curing Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000010792 warming Methods 0.000 description 17
- 238000010992 reflux Methods 0.000 description 11
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 10
- 239000012467 final product Substances 0.000 description 10
- 150000003613 toluenes Chemical class 0.000 description 6
- 238000013459 approach Methods 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
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- 229920000642 polymer Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
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- 239000011347 resin Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- SIFZHHAXBBNVNK-UHFFFAOYSA-N 2-hydroxyethyl 2-methylprop-2-enoate;5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane Chemical compound CC(=C)C(=O)OCCO.CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 SIFZHHAXBBNVNK-UHFFFAOYSA-N 0.000 description 1
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 1
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- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
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- Macromonomer-Based Addition Polymer (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
A preparation method of polyurethane acrylate oligomer surface modified silica belongs to the technical field of nanoparticle surface modification. The method provided by the invention comprises steps of: first synthesizing nano silica by a sol-gel method, and modifying the nano silica with an amino silane coupling agent; reacting acrylate macromonomers with diisocyanate monomers to synthesize an isocyanate group-terminated polyurethane acrylate oligomer; and then reacting the oligomer with the amino silane coupling agent modified silica particles to obtain oligomer surface modified silica. The oligomer modified silica has good dispersion and stability in organic solvents, such as toluene and ethyl acetate and can be used as an additive and a crosslinking agent in the fields of photocuring coating, adhesive, plastic, rubber and novel nano composite material, with promising application prospect.
Description
Technical field
The present invention relates to a kind of preparation method of novel oligopolymer surface modification silicon-dioxide, mainly relate to a kind of preparation method of urethane acrylate quasi-oligomer surface modification silicon-dioxide.Belong to nano particle surface modifying technical field.
Technical background
In recent years, composite organic-inorganic material is due to organic polymer and inorganic nano-particle sub-feature, there is the incomparable property of other common materials and be subject to the extensive concern of academia and industry member, become gradually the focus of current research, but the compatibility problem of organic polymer and inorganic nano-particle is a large bottleneck that is restricting its performance excellent properties always, and inorganic nano-particle is carried out to surface modification, be to solve its dispersiveness in organic substrate and the effective way of consistency.
Because inorganic nano-particle silicon-dioxide is cheap and easy to get, there is the character such as high rigidity, low refractive index, it is inorganic phase comparatively conventional in composite organic-inorganic material, at present it is carried out to surface modifying method of a great variety, comparatively popular small molecules properties-correcting agent mainly contains tensio-active agent, silane coupling agent etc.; Another kind of macromole properties-correcting agent is mainly polymer surface modification, by the whole bag of tricks and means (as controlled living polymerization), polymer graft is carried out to direct chemical reaction or by adsorption by hydrogen bond, forms brush structure or nucleocapsid structure to silica sphere.
But because polymer segment is longer, easily on nano-silicon dioxide particle surface, produce steric hindrance, the more difficult silica sphere that is grafted to; In silica particle surface initiating activity polymerization (as ATRP, RAFT), although can improve its percentage of grafting, its reaction process is very complicated loaded down with trivial details again.And oligopolymer is because segment is shorter, the polymkeric substance of long-chain section relatively, more easily and silica sphere radical reaction, and grafting method is simple.Therefore selecting suitable oligopolymer to carry out surface modification to silicon-dioxide, is comparatively novelty and feasible modified method of a current class.On the other hand, the related polymkeric substance monomer used of polymer surface modification mostly also is vinyl monomer at present, for condensation type polymer, but reports less.The present invention has attempted synthetic a kind of isocyanate-terminated urethane acrylate quasi-oligomer, this oligopolymer is because it is synthetic easy, in segment, contain again the segment of isocyanates and esters of acrylic acid, preliminary study shows, the silicon-dioxide after this quasi-oligomer modification has good consistency with dispersed in light-cured polyurethane resin.
Summary of the invention
The object of this invention is to provide a kind of preparation method of urethane acrylate quasi-oligomer surface modification silicon-dioxide, be grafted to the oligopolymer of nano-silica surface because end contains the two keys of functional groups, can with two key generation curing cross-linkeds of light-cured polyurethane resin, also can with acrylic monomer copolymerization; On the other hand, in the segment of this oligopolymer, contain the segment of isocyanates and esters of acrylic acid, can make the silicon dioxide granule of modification better be dispersed in the resin of above-mentioned two kinds of systems, can effectively improve the mechanical property of resin and surface property as hardness, wear-resisting, damage resistant etc.
Technical scheme of the present invention: a kind of preparation method of urethane acrylate quasi-oligomer surface modification silicon-dioxide, step is:
(1) sol-gel method synthesis of nano silicon-dioxide and modification thereof: by volume for 53.6:3.1:1:2 takes ammoniacal liquor, deionized water, the tetraethyl orthosilicate that dehydrated alcohol, concentration are 28%, said components is mixed, 50 ℃ of stirring reactions of constant temperature 24 hours, obtain silicon-dioxide ethanolic soln; In above-mentioned silicon-dioxide ethanolic soln, add silane coupling agent, silane coupling agent: tetraethyl orthosilicate volume ratio be 0.1:1 ~ 1:1; 50 ℃ of stirring reactions of constant temperature 24 hours, obtain silane-modified silicon-dioxide after centrifuge washing repeatedly with ethanol;
(2) isocyanate-terminated urethane acrylate quasi-oligomer is synthetic: the proportioning that is 1.1:1 by isocyanate monomers and acrylic ester monomer mol ratio, acrylic ester monomer is slowly added drop-wise in the isocyanate monomers that is added with catalyzer, 50 ℃ of stirring reactions of constant temperature 2 ~ 2.5 hours, obtain isocyanate-terminated urethane acrylate quasi-oligomer;
Described catalyzer is selected dibutyltin dilaurate or stannous octoate; Its consumption is 0.05%-0.5% of isocyanate monomers and acrylic ester monomer quality sum;
(3) urethane acrylate quasi-oligomer surface modification silicon-dioxide is synthetic: by ultrasonic silicon-dioxide silane-modified in above-mentioned steps (1), be scattered in dehydration acetone, by silane-modified silicon-dioxide: the proportioning that the mass ratio of isocyanate-terminated urethane acrylate quasi-oligomer is 1:1 ~ 1:10 adds the isocyanate-terminated urethane acrylate quasi-oligomer of step (2) gained wherein, normal-temperature reaction 3 hours, obtains urethane acrylate quasi-oligomer surface modification silicon-dioxide after centrifuge washing.
In step (1), in gained silicon-dioxide ethanolic soln, silicon-dioxide particle size range is 20nm-8000nm, and silicon-dioxide particle diameter changes with the variation of each component mol ratio.
Described in step (1), silane coupling agent is selected: γ-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl triethoxysilane, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl methyldiethoxysilane, anilinomethyl trimethoxy silane, anilinomethyl triethoxysilane, the one in γ-aminoethyl aminopropyl trimethoxysilane.
Described in step (2), isocyanate monomers is selected isophorone diisocyanate, oneself two support vulcabond, Methylcyclohexyl diisocyanate, tolylene diisocyanate, the one in 2,2,4-trimethylammonium hexamethylene diisocyanate.
Described in step (2), acrylic ester monomer is selected PEG acrylate, PEG methacrylic ester, PEG dimethacrylate, PEG ethyl propylene acid esters, hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, the one in ethylacrylic acid hydroxyl ethyl ester, tripropylene glycol diacrylate, pentaerythritol triacrylate, its molecular weight ranges is 100-2000.
Beneficial effect of the present invention: preparation method's tool compared with existing modification technology method of a kind of urethane acrylate quasi-oligomer of the present invention surface modification silicon-dioxide has the following advantages: the isocyanate-terminated urethane acrylate quasi-oligomer of selecting has lower molecular weight, segment is shorter, is easily grafted to silica particle surface; The silica modified technique of oligopolymer surface modification is simple, simple operating steps, and reaction is easy to control, reproducible; Silicon-dioxide after this oligopolymer modification can be used as nanometer additive, linking agent has good application prospect in light solidifying coating, tackiness agent, plastics, rubber, novel nano prepare composite.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) figure of silicon-dioxide in embodiment 1.
Fig. 2 is transmission electron microscope (TEM) figure of silane-modified silicon-dioxide in embodiment 1.
Fig. 3 is transmission electron microscope (TEM) figure of oligopolymer improved silica in embodiment 1.
Fig. 4 is that in embodiment 5, oligopolymer improved silica is scattered in scanning electron microscope (SEM) figure in urethane resin.
Embodiment
In order to explain better, below in conjunction with specific embodiment, the present invention is further explained in detail the present invention.
Embodiment 1
(1) sol-gel method synthetic silica and modification thereof: add successively dehydrated alcohol 600mL in the 1000mL three-necked flask that agitator, thermometer and reflux condensing tube are housed, concentration is 28% ammoniacal liquor 34.8mL, deionized water 11.2mL, be warming up to 50 ℃, then slowly in flask, add tetraethyl orthosilicate 22.4mL, at 50 ℃, after constant temperature stirring reaction 24h, can obtain silicon-dioxide ethanolic soln (particle diameter is about 70nm).Getting 53mL silicon-dioxide ethanolic soln joins in 100mL three-necked flask, be warming up to 50 ℃, slowly drip 3-aminopropyl triethoxysilane (APTES) 0.2mL, after 50 ℃ of stirring reaction 24h of constant temperature, dehydrated alcohol centrifuge washing 3 times repeatedly, ultrasonic being distributed in dehydration acetone, the silicon-dioxide that gets final product silane-modifiedly.
(2) isocyanate-terminated urethane acrylate quasi-oligomer is synthetic: agitator is being housed, in the 100mL three-necked flask of thermometer and reflux condensing tube, add 0.055mol(12.4g) isophorone diisocyanate (IPDI), be warming up to 50 ℃, then by 0.05mol(18g) PEG methacrylic ester (PEGMMA) is slowly added drop-wise in three-necked flask, add a catalyzer dibutyltin dilaurate (about 0.025g), reaction 2-2.5 hour, by Di-n-Butyl Amine method, survey the content of NCO, stopped reaction when NCO content approaches theoretical value, get final product to obtain oligopolymer PEG methacrylic ester-isophorone-vulcabond (PEGMMA-IPDI).The weight-average molecular weight of wherein said PEG methacrylic ester is 360.
(3) urethane acrylate quasi-oligomer surface modification silicon-dioxide is synthetic: get oligopolymer (PEGMMA-IPDI) 3g in above-mentioned steps (2), join in step (1) and be dispersed with in the acetone of silane-modified silicon-dioxide, after 25 ℃ of stirring reaction 3h of constant temperature, with dehydration acetone centrifuge washing 3 times repeatedly, and ultrasonic being distributed in dehydrated toluene, can obtain oligopolymer (PEGMMA-IPDI) surface modification silicon-dioxide.Wherein said centrifugal rotational speed is 10000 revs/min, and each centrifugation time is 15 minutes.
Embodiment 2
(1) sol-gel method synthetic silica and modification thereof: add successively dehydrated alcohol 600mL in the 1000ml three-necked flask that agitator, thermometer and reflux condensing tube are housed, ammoniacal liquor 34.8mL, deionized water 11.2mL, be warming up to 50 ℃, then slowly in flask, add tetraethyl orthosilicate 22.4mL, at 50 ℃, after constant temperature stirring reaction 24h, can obtain silicon-dioxide ethanolic soln (particle diameter is about 70nm).Getting 53mL silicon-dioxide ethanolic soln joins in 100mL three-necked flask, be warming up to 50 ℃, slowly drip 3-aminopropyl triethoxysilane (APTES) 0.2ml, after 50 ℃ of stirring reaction 24h of constant temperature, dehydrated alcohol centrifuge washing 3 times repeatedly, ultrasonic being distributed in dehydration acetone, the silicon-dioxide that gets final product silane-modifiedly.
(2) isocyanate-terminated urethane acrylate quasi-oligomer is synthetic: agitator is being housed, in the 100ml three-necked flask of thermometer and reflux condensing tube, add 0.055mol(12.4g) isophorone diisocyanate (IPDI), be warming up to 50 ℃, then by 0.05mol(40g) PEG methacrylic ester (PEGMMA) is slowly added drop-wise in three-necked flask, add a catalyzer dibutyltin dilaurate (about 0.025g), reaction 2-2.5 hour, by Di-n-Butyl Amine method, survey the content of NCO, stopped reaction when NCO content approaches theoretical value, get final product to obtain oligopolymer PEG methacrylic ester-isophorone-vulcabond (PEGMMA-IPDI).The weight-average molecular weight of wherein said PEG methacrylic ester is 800.
(3) urethane acrylate quasi-oligomer surface modification silicon-dioxide is synthetic: get oligopolymer (PEGMMA-IPDI) 4g in above-mentioned steps (2), join in step (1) and be dispersed with in the acetone of silane-modified silicon-dioxide, after 25 ℃ of stirring reaction 3h of constant temperature, with dehydration acetone centrifuge washing 3 times repeatedly, and ultrasonic being distributed in dehydrated toluene, can obtain oligopolymer (PEGMMA-IPDI) surface modification silicon-dioxide.Wherein said centrifugal rotational speed is 10000 revs/min, and each centrifugation time is 15 minutes.
Embodiment 3
(1) sol-gel method synthetic silica and modification thereof: add successively dehydrated alcohol 600mL in the 1000mL three-necked flask that agitator, thermometer and reflux condensing tube are housed, ammoniacal liquor 34.8mL, deionized water 11.2mL, be warming up to 50 ℃, then slowly in flask, add tetraethyl orthosilicate 22.4mL, at 50 ℃, after constant temperature stirring reaction 24h, can obtain silicon-dioxide ethanolic soln (particle diameter is about 70nm).Getting 53mL silicon-dioxide ethanolic soln joins in 100mL there-necked flask, be warming up to 50 ℃, slowly drip 3-aminopropyl triethoxysilane (APTES) 0.2ml, after 50 ℃ of stirring reaction 24h of constant temperature, dehydrated alcohol centrifuge washing 3 times repeatedly, ultrasonic being distributed in dehydration acetone, the silicon-dioxide that gets final product silane-modifiedly.
(2) isocyanate-terminated urethane acrylate quasi-oligomer is synthetic: agitator is being housed, in the 100ml three-necked flask of thermometer and reflux condensing tube, add 0.055mol(12.4g) isophorone diisocyanate (IPDI), be warming up to 50 ℃, then by 0.05mol(6.7g) hydroxyethyl methylacrylate (HEMA) is slowly added drop-wise in there-necked flask, add 2 catalyzer dibutyltin dilaurates (about 0.05g), reaction 2-2.5 hour, by Di-n-Butyl Amine method, survey the content of NCO, stopped reaction when NCO content approaches theoretical value, get final product to obtain oligopolymer hydroxyethyl methylacrylate-isophorone diisocyanate (HEMA-IPDI).
(3) urethane acrylate quasi-oligomer surface modification silicon-dioxide is synthetic: get oligopolymer (HEMA-IPDI) 2g in above-mentioned steps (2), join in step (1) and be dispersed with in the acetone of silane-modified silicon-dioxide, after 25 ℃ of stirring reaction 3h of constant temperature, with dehydration acetone centrifuge washing 3 times repeatedly, and ultrasonic being distributed in dehydrated toluene, can obtain oligopolymer (HEMA-IPDI) surface modification silicon-dioxide.Wherein said centrifugal rotational speed is 10000 revs/min, and each centrifugation time is 15 minutes.
Embodiment 4
(1) sol-gel method synthetic silica and modification thereof: add successively dehydrated alcohol 600mL in the 1000ml three-necked flask that agitator, thermometer and reflux condensing tube are housed, ammoniacal liquor 34.8mL, deionized water 11.2mL, be warming up to 50 ℃, then slowly in flask, add tetraethyl orthosilicate 22.4mL, at 50 ℃, after constant temperature stirring reaction 24h, can obtain silicon-dioxide ethanolic soln (particle diameter is about 70nm).Getting 53ml silicon-dioxide ethanolic soln joins in 100mL three-necked flask, be warming up to 50 ℃, slowly drip 3-aminopropyl triethoxysilane (APTES) 0.2ml, after 50 ℃ of stirring reaction 24h of constant temperature, dehydrated alcohol centrifuge washing 3 times repeatedly, ultrasonic being distributed in dehydration acetone, the silicon-dioxide that gets final product silane-modifiedly.
(2) isocyanate-terminated urethane acrylate quasi-oligomer is synthetic: agitator is being housed, in the 100ml three-necked flask of thermometer and reflux condensing tube, add 0.055mol(12.4g) isophorone diisocyanate (IPDI), be warming up to 50 ℃, then by 0.05mol(23.75g) PEG acrylate (PEGMA) is slowly added drop-wise in there-necked flask, add a catalyzer dibutyltin dilaurate (about 0.025g), reaction 2-2.5 hour, by Di-n-Butyl Amine method, survey the content of NCO, stopped reaction when NCO content approaches theoretical value, get final product to obtain oligopolymer PEG acrylate-isophorone-vulcabond (PEGMA-IPDI).The weight-average molecular weight of wherein said PEG acrylate is 475.
(3) urethane acrylate quasi-oligomer surface modification silicon-dioxide is synthetic: get oligopolymer (PEGMA-IPDI) 4g in above-mentioned steps (2), join in step (1) and be dispersed with in the acetone of silane-modified silicon-dioxide, after 25 ℃ of stirring reaction 3h of constant temperature, with dehydration acetone centrifuge washing 3 times repeatedly, and ultrasonic being distributed in dehydrated toluene, can obtain oligopolymer (PEGMA-IPDI) surface modification silicon-dioxide.Wherein said centrifugal rotational speed is 10000 revs/min, and each centrifugation time is 15 minutes.
Embodiment 5
(1) sol-gel method synthetic silica and modification thereof: add successively dehydrated alcohol 600mL in the 1000ml three-necked flask that agitator, thermometer and reflux condensing tube are housed, ammoniacal liquor 34.8mL, deionized water 11.2mL, be warming up to 50 ℃, then slowly in flask, add tetraethyl orthosilicate 22.4mL, at 50 ℃, after constant temperature stirring reaction 24h, can obtain silicon-dioxide ethanolic soln (particle diameter is about 70nm).Getting 53mL silicon-dioxide ethanolic soln joins in 100mL three-necked flask, be warming up to 50 ℃, slowly drip 3-aminopropyl triethoxysilane (APTES) 0.2ml, after 50 ℃ of stirring reaction 24h of constant temperature, dehydrated alcohol centrifuge washing 3 times repeatedly, ultrasonic being distributed in dehydration acetone, the silicon-dioxide that gets final product silane-modifiedly.
(2) isocyanate-terminated urethane acrylate quasi-oligomer is synthetic: agitator is being housed, in in the 100mL three-necked flask of thermometer and reflux condensing tube, add 0.055mol(12.4g) isophorone diisocyanate (IPDI), be warming up to 50 ℃, then by 0.05mol(18g) PEG methacrylic ester (PEGMMA) is slowly added drop-wise in three-necked flask, add a catalyzer dibutyltin dilaurate (about 0.025g), reaction 2-2.5 hour, by Di-n-Butyl Amine method, survey the content of NCO, stopped reaction when NCO content approaches theoretical value, get final product to obtain oligopolymer PEG acrylate-isophorone-vulcabond (PEGMMA-IPDI).The weight-average molecular weight of wherein said PEG methacrylic ester is 360.
(3) urethane acrylate quasi-oligomer surface modification silicon-dioxide is synthetic: get oligopolymer (PEGMMA-IPDI) 4g in above-mentioned steps (2), join in step (1) and be dispersed with in the acetone of silane-modified silicon-dioxide, after 25 ℃ of stirring reaction 3h of constant temperature, with dehydration acetone centrifuge washing 3 times repeatedly, and ultrasonic being distributed in dehydrated toluene, can obtain oligopolymer (PEGMMA-IPDI) surface modification silicon-dioxide.Wherein said centrifugal rotational speed is 10000 revs/min, and each centrifugation time is 15 minutes.
(4) solvent-borne type ultraviolet curing urethane resin is synthetic: in the 250mL tetra-neck flasks that agitator, thermometer and reflux condensing tube are housed, add 14.5g isophorone diisocyanate (IPDI), under room temperature, stir while drip the polycarbonate diol (PCD-800 of 32g with dropping funnel, molecular-weight average is 800) and the mixing solutions of 0.05g catalyzer dibutyltin dilaurate, rate of addition is controlled in 1h.Dropwise at 50 ℃ of reaction 2-2.5h, and add a small amount of dehydrated toluene to reduce system viscosity, be then warming up to 70 ℃ and reach theoretical value (measuring gained by two positive fourth case back titration methods) until measure NCO group, obtain the base polyurethane prepolymer for use as of NCO end-blocking.The 5.4g hydroxyethyl methylacrylate (HEMA) that contains 0.01g stopper MEHQ is added drop-wise in base polyurethane prepolymer for use as, and reaction at 70 ℃ of constant temperature, until can't detect NCO at 2265cm with infrared spectra
-1the absorption peak at place, obtains solvent-borne type ultraviolet curing urethane resin.
(5) preparation of silicon dioxide-poly-ammonia ester ultraviolet light polymerization composite membrane: by the nano silicon of above-mentioned oligopolymer surface modification, join in the flat centrifuge tube that contains the above-mentioned urethane resin of 3.5g, under room temperature, after blended under agitation for some time, add 0.04g light trigger 184, to be mixedly pour in rectangle glass mould after evenly, put at 40 ℃, baking oven and keep 10-12h, be warming up to again 60 ℃ and keep 1h, carry out while hot ultraviolet light polymerization, obtain silicon dioxide-poly-ammonia ester ultraviolet light polymerization composite membrane.
Claims (5)
1. a preparation method for urethane acrylate quasi-oligomer surface modification silicon-dioxide, is characterized in that carrying out according to following steps:
(1) sol-gel method synthesis of nano silicon-dioxide and modification thereof: by volume for 53.6:3.1:1:2 takes ammoniacal liquor, deionized water, the tetraethyl orthosilicate that dehydrated alcohol, concentration are 28%, said components is mixed, 50 ℃ of stirring reactions of constant temperature 24 hours, obtain silicon-dioxide ethanolic soln; In above-mentioned silicon-dioxide ethanolic soln, add silane coupling agent, silane coupling agent: tetraethyl orthosilicate volume ratio be 0.1:1 ~ 1:1; 50 ℃ of stirring reactions of constant temperature 24 hours, obtain silane-modified silicon-dioxide with after ethanol centrifuge washing 3 times;
(2) isocyanate-terminated urethane acrylate quasi-oligomer is synthetic: the proportioning that is 1.1:1 by isocyanate monomers and acrylic ester monomer mol ratio, acrylic ester monomer is slowly added drop-wise in the isocyanate monomers that is added with catalyzer, 50 ℃ of stirring reactions of constant temperature 2 ~ 2.5 hours, obtain isocyanate-terminated urethane acrylate quasi-oligomer;
Described catalyzer is selected dibutyltin dilaurate or stannous octoate; Its consumption is 0.05%-0.5% of isocyanate monomers and acrylic ester monomer quality sum;
(3) urethane acrylate quasi-oligomer surface modification silicon-dioxide is synthetic: by ultrasonic silicon-dioxide silane-modified in above-mentioned steps (1), be scattered in dehydration acetone, by silane-modified silicon-dioxide: the proportioning that the mass ratio of isocyanate-terminated urethane acrylate quasi-oligomer is 1:1 ~ 1:10 adds the isocyanate-terminated urethane acrylate quasi-oligomer of step (2) gained wherein, normal-temperature reaction 3 hours, obtains urethane acrylate quasi-oligomer surface modification silicon-dioxide after centrifuge washing.
2. the preparation method of urethane acrylate quasi-oligomer surface modification silicon-dioxide according to claim 1, it is characterized in that in the middle gained silicon-dioxide ethanolic soln of step (1), silicon-dioxide particle size range is 20nm-8000nm, silicon-dioxide particle diameter changes with the variation of each component mol ratio.
3. the preparation method of urethane acrylate quasi-oligomer surface modification silicon-dioxide according to claim 1, it is characterized in that described in step (1), silane coupling agent is selected: γ-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl triethoxysilane, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl methyldiethoxysilane, anilinomethyl trimethoxy silane, anilinomethyl triethoxysilane, one in γ-aminoethyl aminopropyl trimethoxysilane.
4. the preparation method of urethane acrylate quasi-oligomer surface modification silicon-dioxide according to claim 1, it is characterized in that described in step (2), isocyanate monomers is selected isophorone diisocyanate, oneself two support vulcabond, Methylcyclohexyl diisocyanate, tolylene diisocyanate, one in 2,2,4-trimethylammonium hexamethylene diisocyanate.
5. the preparation method of urethane acrylate quasi-oligomer surface modification silicon-dioxide according to claim 1, it is characterized in that described in step (2), acrylic ester monomer is selected PEG acrylate, PEG methacrylic ester, PEG ethyl propylene acid esters, hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, the one in ethylacrylic acid hydroxyl ethyl ester, pentaerythritol triacrylate, its molecular weight ranges is 100-2000.
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